EP0402315A2 - Verfahren zur Herstellung eines metallischen Musters auf einem Substrat - Google Patents

Verfahren zur Herstellung eines metallischen Musters auf einem Substrat Download PDF

Info

Publication number
EP0402315A2
EP0402315A2 EP90810391A EP90810391A EP0402315A2 EP 0402315 A2 EP0402315 A2 EP 0402315A2 EP 90810391 A EP90810391 A EP 90810391A EP 90810391 A EP90810391 A EP 90810391A EP 0402315 A2 EP0402315 A2 EP 0402315A2
Authority
EP
European Patent Office
Prior art keywords
resin film
parts
electrodeposited
resist
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90810391A
Other languages
English (en)
French (fr)
Other versions
EP0402315A3 (de
Inventor
Christopher Paul Dr. Banks
Edward Dr. Irving
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0402315A2 publication Critical patent/EP0402315A2/de
Publication of EP0402315A3 publication Critical patent/EP0402315A3/de
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0562—Details of resist
    • H05K2203/0582—Coating by resist, i.e. resist used as mask for application of insulating coating or of second resist
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
    • H05K2203/1333—Deposition techniques, e.g. coating
    • H05K2203/135—Electrophoretic deposition of insulating material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49117—Conductor or circuit manufacturing
    • Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
    • Y10T29/49155—Manufacturing circuit on or in base

Definitions

  • the board comprising a copper clad base laminate, has holes drilled where desired, a resist is coated on the copper in a predetermined pattern, using screen printing or photoimaging techniques, to give a board having bare copper in some areas and copper coated by the resist in remaining areas, the bare copper is then plated with a tin-lead alloy, the resist is then removed, the copper thereby exposed is etched using an etchant which does not remove the tin-lead alloy, and the alloy is finally removed using a tin-lead alloy stripper.
  • the resist present as a coating on the initial substrate may be an epoxide resin applied by a screen printing process and then cured.
  • the resist is a photoresist coated in selected areas by applying it uniformly to the substrate, which is usually a copper-clad laminate, subjecting it to actinic radiation in a predetermined pattern and then removing exposed or unexposed areas according to whether the photoresist is positive or negative respectively.
  • Positive and negative photoresists for use in making printed circuit boards are well known materials and any of them may be used. They can be strippable under aqueous conditions or by means of an organic solvent. Another layer of copper or a layer of another metal such as nickel may be deposited on bare copper areas before electrodeposition in stage (i).
  • Suitable acrylic resins include copolymers of at least one acrylic ester such as an alkyl or hydroxyalkyl acrylate or methacrylate with an ethylenically unsaturated monomer containing a salt-forming group, such as an acrylic monomer containing a carboxyl or an amino group and, optionally, another ethylenically unsaturated monomer.
  • an acrylic ester such as an alkyl or hydroxyalkyl acrylate or methacrylate
  • an ethylenically unsaturated monomer containing a salt-forming group such as an acrylic monomer containing a carboxyl or an amino group and, optionally, another ethylenically unsaturated monomer.
  • Suitable polyurethanes include adducts of hydroxyl-terminated polyurethanes with polycarboxylic acid anhydrides.
  • Suitable polyesters include carboxyl-terminated polyesters derived from polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol or butane-1,4-diol with polycarboxylic acids such as glutaric, adipic, maleic, tetrahydrophthalic and phthalic acids or esterifying derivatives thereof.
  • Preferred acrylic polymers include copolymers of at least one monoacrylic monomer containing a carboxyl group and at least one monoacrylic ester, optionally together with at least one other vinyl monomer.
  • Suitable carboxyl-containing monoacrylic monomers from which the copolymers may be derived include acrylic acid, methacrylic acid and adducts of a hydroxyalkyl acrylate or methacrylate with a polycarboxylic acid anhydride.
  • Acrylic and methacrylic acids are particularly preferred carboxyl-containing acrylic monomers.
  • Isocyanate-blocking agents are well known and include alcohols, phenols, mercaptans, primary and secondary amines, oximes, triazoles, pyrazoles and lactams. Preferred such blocking agents are oximes and lactams.
  • a particularly preferred reactive group-containing monoacrylic ester is 2-hydroxyethyl methacrylate.
  • the optional vinyl monomer which may be copolymerised with the carboxyl-containing acrylic monomer and the monoacrylic ester may be, for example, a vinyl ester such as vinyl acetate, a vinyl halide such as vinyl chloride or, preferably, a styrene, such as styrene itself, alpha-methylstyrene or p-chlorostyrene, styrene itself being particularly preferred.
  • the optional vinyl monomer which may be copolymerised with the tertiary amine group-containing monoacrylic monomer and the reactive group-containing monoacrylic ester may be, for example, an alkyl acrylate or methacrylate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the corresponding methacrylates, a vinyl ester such as vinyl acetate, a vinyl halide such as vinyl chloride or a styrene such as styrene, alpha-methyl styrene or p-chlorostyrene.
  • the alkyl acrylates and methacrylates and styrene are preferred.
  • acrylic polymers for use in the method of the invention are copolymers of (a) acrylic acid, methacrylic acid or 2-(dimethylamino)ethyl methacrylate with (b) a hydroxyalkyl acrylate or methacrylate and, optionally, (c) at least one further vinyl monomer, preferably selected from alkyl acrylates, alkyl methacrylates, styrene and mixtures of two or more thereof.
  • the acrylic polymers may be prepared by conventional polymerisation processes using free radical polymerisation initiators such as peroxides or azo compounds, usually to give polymers having a number average molecular weight of 5000 or more, preferably 5000 to 50,000.
  • free radical polymerisation initiators such as peroxides or azo compounds
  • the monomers may be heated with the initiator in solution in an organic solvent, preferably a solvent which is miscible with the medium from which the polymer is to be electrodeposited.
  • Conventional chain transfer agents such as tert.dodecyl mercaptan can be used when desired.
  • Preferred adducts of an epoxide resin with an amine are adducts of a polyglycidyl ether, which may be of a polyhydric phenol or a polyhydric alcohol, with a secondary monoamine.
  • Suitable polyglycidyl ethers include those of dihydric alcohols such as butane-1,4-diol, neopentyl glycol, hexamethylene glycol, oxyalkylene glycols and polyoxyalkylene glycols, and trihydric alcohols such as glycerol, 1,1,1-trimethylolpropane and adducts of these alcohols with ethylene oxide or propylene oxide.
  • polyglycidyl ethers of polyhydric alcohols are usually advanced, i.e. converted into longer chain higher molecular weight polyglycidyl ethers, for example by reaction with a dihydric alcohol or phenol, so that the resulting polyglycidyl ethers give adducts with suitable electrodepositable film-forming properties on reaction with the secondary monoamine.
  • Preferred polyglycidyl ethers are those of polyhydric phenols, including bisphenols such as bisphenol F, bisphenol A and tetrabromobisphenol A and phenolic novolak resins such as phenol-formaldehyde or cresol-formaldehyde novolak resins.
  • polyglycidyl ethers of phenols may have been advanced, for example by reaction with dihydric alcohols or phenols such as those hereinbefore described.
  • Particularly preferred polyglycidyl ethers are polyglycidyl ethers of bisphenol A advanced by reaction with bisphenol A.
  • Secondary monoamines suitable for adduct formation with the polyglycidyl ethers include dialkylamines such as diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-octyl­amine and di-n-dodecylamine or nitrogen heterocycles such as piperidine or morpholine.
  • Preferred secondary monoamines are secondary alkanolamines such as diethanolamine, N-methylethanol­amine, N-butylethanolamine, diisopropanolamine, N-methyl­isopropanolamine or di-n-butanolamine.
  • a particularly preferred secondary alkanolamine is diethanolamine.
  • adducts of polyglycidyl ether with a secondary monoamine are adducts of a polyglycidyl ether of a polyhydric phenol, which may have been advanced, with a secondary alkanolamine, while particularly preferred such adducts are those of a polyglycidyl ether of bisphenol A, advanced by reaction with bisphenol A, with diethanolamine.
  • Electrodeposition of the organic resin may be carried out using conventional procedures.
  • the electrodepositable resin optionally together with conventional additives such as pigments, dyes, fillers and plasticizers, can be dissolved or dispersed in an aqueous medium, which may contain a minor amount of an organic solvent, together with an acid or base to at least partially neutralise salt-forming groups on the resin.
  • the aqueous electrodeposition medium generally contains from 2 to 60%, preferably from 5 to 25%, by weight of the resin.
  • the metallic surface on which the resin film is to be electrodeposited can be immersed in the electrodeposition medium as an anode or cathode, depending on whether the resin is anodically or cathodically depositable, another electrode of opposite charge immersed in the medium and a current passed between the electrodes to electrodeposit the resin on the required electrode.
  • Suitable hardening agents include photocurable materials, preferably a photocurable material having, on average, more than one polymerisable acrylic group per molecule, together with a photoinitiator therefor.
  • Suitable such acrylic materials include esters of acrylic or methacrylic acid, or a carboxyl-­containing adduct of a hydroxyalkyl acrylate or methacrylate and a polycarboxylic acid anhydride, with a polyhydric alchol, which can be a low molecular weight alcohol or a film-forming resin, or with an epoxide resin; and acrylic urethane reaction products of isocyanate-terminated polyurethane prepolymers with a hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
  • acrylates and methacrylates are commercially available. Those that are not can be made by conventional processes, for example by esterifying the polyhydric alcohol with acrylic or methacrylic acid or an esterifying derivative thereof such as acryloyl chloride or methacryloyl chloride.
  • Photoinitiators for use with curable acrylic materials are well known and many different types are commercially available. Any of the known types can be used in a conventional amount, generally from 0.1 to 20%, preferably 1 to 10%, by weight of the polymerisable material.
  • the photoinitiator may be an aromatic carbonyl compound, for example a benzoin alkyl ether such as the isopropyl or n-butyl ether, an alpha-substituted acetophenone, for example a benzil dialkyl ketal such as benzil dimethyl ketal, an alpha-halo-acetophenone such as trichloromethyl p-tert.butylphenyl ketone, an alpha-aminoacetophenone such as dimethylaminomethyl phenyl ketone and morpholinomethyl phenyl ketone, a dialkoxyacetophenone such as diethoxyacetophenone, or an alpha-hydroxyacetophenone such as 1-
  • the aminoplast resins are used together with a curing catalyst which releases an acid on heating;
  • curing catalysts are well known and include ammonium and amine salts of strong inorganic and organic acids, e.g. ammonium chloride, ammonium sulphate, and salts of p-toluenesulphonic acid with amines such as triethylamine, triethanolamine and morpholine, the morpholine salt of p-toluenesulphonic acid being particularly preferred.
  • the hardening agent may be a material having blocked isocyanate groups, i.e. isocyanate groups blocked by reaction with an active hydrogen atom so that the resulting blocked group is unreactive at ambient temperatures but is reactive at elevated temperatures.
  • blocked isocyanate materials suitable for use in the method of the invention may be any of the known materials, including those prepared by reacting a polyisocyanate, i.e.
  • a material having, per average molecule, more than one isocyanate group with a blocking agent having an alcoholic or phenolic hydroxyl group, a mercaptan group, a primary or secondary amino group, an imidazole group, an oxime group, a triazole group, a pyrazole group or a lactam group.
  • the blocking reactions may be carried out at 30-110°C in an inert solvent.
  • the material having more than one isocyanate group per molecule may be an isocyanate-terminated prepolymer; preferably it is an aliphatic, cycloaliphatic or aromatic diisocyanate such as 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene and hexamethylene diisocyanates, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate), m- and p-phenylene diisocyanates, 2,4- and 2,6-tolylene diisocyanates, 1-chloro-2,4-diisocyanatobenzene, 1,4-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate and 4,4′-diphenylether diisocyanate.
  • the aromatic diisocyanates are preferred, especially tolylene-2,4-diisocyanate and 4,
  • the polyisocyanate is usually reacted first with the oxime and then with the polyhydric alcohol.
  • Particularly preferred blocked isocyanates used in the method of the invention are tolylene-2,4-diisocyanate blocked by reaction first with methylethyl ketoxime, then with either butane-1,4-diol or 1,1,1-trimethylolpropane, and 4,4′-diphenylmethane diisocyanate blocked by reaction with methylethyl ketoxime.
  • the aqueous solvent in which the hardening agent is dissolved or dispersed is usually a mixture of water with a water-miscible organic solvent such as ethanol, 2-ethoxyethanol, 2-n-butoxyethanol, or diethyleneglycol monobutyl ether (butyl digol) to assist diffusion of the hardening agent into the surface of the electrodeposited organic resin film.
  • a water-miscible organic solvent such as ethanol, 2-ethoxyethanol, 2-n-butoxyethanol, or diethyleneglycol monobutyl ether (butyl digol)
  • a suitable solvent which does not dissolve the electro­deposited film can be found by routine experimentation.
  • Both this solvent and the solvent used subsequently to remove the electrodeposited film can be selected from halohydrocarbons such as 1,1,1-trichloroethane and dichloromethane, hydroxylic solvents such as ethanol, 2-n-butoxyethanol and diethyleneglycol monobutyl ether (butyl digol), esters such as 2-ethoxyethyl acetate and propylene carbonate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as tetrahydrofuran, lactones such as butyrolactone and mixtures of two or more thereof.
  • halohydrocarbons such as 1,1,1-trichloroethane and dichloromethane
  • hydroxylic solvents such as ethanol, 2-n-butoxyethanol and diethyleneglycol monobutyl ether (butyl digol)
  • the resist is removed in step (iv) using an aqueous solvent and at least part of the electrodeposited film is removed using an organic solvent, the resist and film being chosen accordingly.
  • the metal exposed by removal of the resist usually copper, may be removed by any well known etchant such as ferric chloride, hydrogen peroxide/phosphoric acid, ammonium persulphate or cupric chloride.
  • the substrate has a surface comprising predetermined areas of metal covered by the electro­deposited film and predetermined areas from which the metal has been removed by the etching process.
  • the initial substrate is a copper-clad plastics laminate
  • the surface comprises predetermined areas of copper covered by the electrodeposited resin film and areas in which the laminate base is devoid of copper.
  • a further resist to act for example, as a solder mask is formed in a predetermined pattern over the electrodeposited film, thereby leaving areas of the electrodeposited film uncovered by the further resist and said uncovered areas of the electrodeposited film are then removed.
  • the pattern formation of the further resist can be effected by applying a photocurable resin composition directly in a predetermined pattern using a screen printing technique and irradiating the screen printed layer to effect cure thereof.
  • Photocurable resin compositions which can be applied by screen printing are well known to those skilled in the art of making printed circuit boards.
  • the photocurable resins can be, for example, resins containing polymerisable acrylate or methacrylate ester groups used together with free radical-­generating photoinitiators therefor.
  • Conventional positive and negative photoresists may be used as the further resist. They may be irradiated with actinic radiation in a predetermined pattern and developed using known procedures.
  • the first resist is removed by aqueous solvents
  • the more soluble parts of the irradiated further resist are removed by means of an organic solvent
  • the electrodeposited film underlying those parts is removed by means of an organic solvent used to remove the further resist.
  • the process of the invention is particularly useful in the production of printed circuits, including multilayer circuits having plated through holes or vias.
  • a monomer mixture consisting of styrene (47.5 parts), 2-ethylhexyl acrylate (25 parts), 2-hydroxyethyl methacrylate (20 parts) and 2-(dimethylamino)ethyl methacrylate (7.5 parts) with azobis(isobutyronitrile) (1.5 parts) is added dropwise over 2 hours to 2-n-butoxyethanol (50 parts) stirred under nitrogen at 100°C.
  • the reaction mixture is maintained at 100°C for a further 1 hour and a further charge of azobis(isobutyronitrile) (0.5 part) and 2-n-butoxyethanol (5.5 parts) is added.
  • An epoxide resin prepared by advancing a diglycidyl ether of bisphenol A by reaction with bisphenol A (epoxide content 1.1 equivs/kg, 50 parts) is dissolved in 2-n-butoxyethanol (50 parts) at 120°C.
  • Diethanolamine (5.88 parts) is added dropwise over 15 minutes and the mixture is stirred at 120°C for a further 3 hours, by which time the epoxide content is negligible.
  • the reaction product is cooled to ambient temperature.
  • a monomer mixture consisting of styrene (60 parts), 2-ethylhexyl acrylate (27.5 parts), 2-hydroxyethyl methacrylate (7.5 parts) and 2-(dimethylamino)ethyl methacrylate (5 parts) with azobis(isobutyronitrile) (1.5 parts) is added dropwise over 2 hours to 2-n-butoxyethanol (50 parts) stirred at 120°C.
  • the reaction mixture is maintained at 120°C for a further hour and a further charge of azobis(isobutyronitrile) (0.5 part) and 2-n-­butoxyethanol (5.5 parts) added.
  • An epoxide resin prepared by advancing a diglycidyl ether of bisphenol A by reaction with bisphenol A (epoxide content 1.5 equivs/kg, 50 parts) is dissolved in 2-n-butoxyethanol (50 parts) at 120°C.
  • Diethanolamine (7.67 parts) is added dropwise over 15 minutes and the mixture is stirred at 120°C for a further 3 hours, by which time the epoxide content is negligible.
  • the reaction product is cooled to ambient temperature.
  • the HOECHST HB 1160 DRY FILM STRIPPER used in the Examples is an aqueous mixture of ethanolamine and butoxyethanol and is available from Hoechst U.K. Ltd., Electronic Products Division, Unit 20, Smiths Industrial Estate, Number Avenue, Coventry, CV3 1JR, England.
  • tolylene-2,4-diisocyanate used in the Examples is a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate.
  • the laminate is then immersed for 30 seconds in a bath containing pentaerythritol triacrylate (100 parts), benzil dimethyl ketal (5 parts), water (150 parts) and 2-n-butoxyethanol (245 parts), rinsed in water and dried at 110°C for 5 minutes.
  • the dried laminate is irradiated using a 5kw metal halide lamp at a distance of 75 cm for 4 minutes to harden the surface of the electrodeposited resin film.
  • the laminate is then immersed in an aqueous 20% solution of HOECHST HB 1160 DRY FILM STRIPPER at 50°C. This treatment removes the photoresist leaving the electrodeposited film.
  • the copper exposed by removing the photoresist is etched away in a solution of concentrated sulphuric acid (20 parts) and ammonium persulphate (150 parts) in water (830 parts) at 50°C, after which the laminate is washed in water and dried, to leave a clear pattern, in copper covered with electro­deposited film, on the laminate base.
  • Immersion in a mixture of propylene carbonate (50 parts), gamma-butyrolactone (20 parts) and butyl digol (30 parts) removes the electrodeposited film to leave a clear copper pattern on the laminate base.
  • a copper-clad laminate coated with RISTON 3415 aqueous developable photoresist which has been imaged and developed to form a pattern in the photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode and containing a solution of Resin II (100 parts) and aqueous 20% lactic acid (18.5 parts) in water (409.2 parts).
  • a voltage of 20 volts is applied for one minute, following which the laminate is removed from the bath and rinsed with water.
  • the electrodeposited resin film coats the areas where there is no photoresist and the copper is exposed.
  • the laminate is then immersed for 2 minutes in a bath containing a methylated melamine-formaldehyde resin (substantially hexamethoxymethylmelamine) (100 parts), the morpholine salt of p-toluenesulphonic acid (7.5 parts), 2-n-butoxyethanol (100 parts) and water (292.5 parts), followed by rinsing in water.
  • a methylated melamine-formaldehyde resin substantially hexamethoxymethylmelamine
  • the morpholine salt of p-toluenesulphonic acid 7.5 parts
  • 2-n-butoxyethanol 100 parts
  • water 292.5 parts
  • the laminate is then immersed for 2 minutes in a bath containing a methylated melamine-formaldehyde resin (substantially hexamethoxymethyl melamine) (100 parts), morpholine salt of p-toluenesulphonic acid (7.5 parts), 2-n-butoxyethanol (100 parts) and water (292.5 parts), followed by rinsing in water.
  • a methylated melamine-formaldehyde resin substantially hexamethoxymethyl melamine
  • morpholine salt of p-toluenesulphonic acid 7.5 parts
  • 2-n-butoxyethanol 100 parts
  • water 292.5 parts
  • the copper exposed by removing the photoresist is etched away in a solution of concentrated sulphuric acid (20 parts) and ammonium persulphate (150 parts) in water (830 parts) at 50°C, after which the laminate is washed with water and dried, to leave a clear pattern, in copper covered with the electrodeposited film, on the laminate base.
  • Immersion in a mixture of propylene carbonate (50 parts), gamma-butyrolactone (20 parts) and butyl digol (30 parts) removes the electrodeposited film to leave a clear copper pattern on the laminate base.
  • Example 2 The procedure of Example 2 is repeated, but using an electrodeposition bath containing a solution of Resin I (100 parts) and aqueous 20% lactic acid (6.7 parts) in water (493.3 parts) instead of the electrodeposition bath used in Example 2 and applying a voltage of 30 volts for one minute instead of 20 volts for one minute. A clear copper pattern on the laminate base is obtained.
  • a copper-clad laminate coated with RISTON 3415 aqueous developable photoresist which has been imaged and developed to form a pattern in the photoresist, is used as the anode in an electrodeposition bath equipped with a stainless steel cathode and containing a solution of Resin III (100 parts) and aqueous 20% potassium hydroxide solution (5 parts) in water (395 parts). After applying a voltage of 60 volts for one minute, the laminate is removed from the bath and rinsed with water. The electrodeposited resin film coats the areas where there is no photoresist and the copper is exposed.
  • the laminate is then immersed for 2 minutes in a bath containing a blocked isocyanate (8 parts, prepared by reacting 2 moles of technical grade tolylene-2,4-diisocyanate first with 2 moles of methylethyl ketoxime, then with 1 mole of 1,1,1-trimethylolpropane), 2-n-butoxyethanol (22 parts) and water (10 parts), followed by rinsing in water.
  • the laminate is then heated at 110°C for 15 minutes to harden the surface of the electrodeposited resin film.
  • the RISTON photoresist is removed by immersing the laminate in an aqueous 20% solution of HOECHST HB 1160 DRY FILM STRIPPER at 50°C.
  • the copper exposed by removing the photoresist is etched away in a solution of concentrated sulphuric acid (20 parts) and ammonium persulphate (150 parts) in water (830 parts) at 50°C, after which the laminate is washed with water and dried, to leave a clear pattern, in copper covered with the electrodeposited film, on the laminate base.
  • Immersion in a mixture of propylene carbonate (50 parts), gamma-butyrolactone (20 parts) and butyl digol (30 parts) removes the electrodeposited film to leave a clear copper pattern on the laminate base.
  • Example 3 The procedure of Example 3 is repeated, but omitting the morpholine salt from the bath in which the laminate is immersed after electrodeposition, increasing the amount of water in this bath to 300 parts, and heating the laminate at 150° for 10 minutes instead of 5 minutes. A clear copper pattern on the laminate base is obtained.
  • a copper-clad laminate coated with RISTON 3415 aqueous developable photoresist which has been imaged and developed to form a pattern in the photoresist, is used as the cathode in an electrodeposition bath equipped with a stainless steel anode and containing a solution of Resin I (100 parts) and aqueous 20% lactic acid (6.7 parts) in water (493.3 parts). After applying a voltage of 80 volts for one minute, the laminate is removed from the bath and rinsed with water. The electrodeposited resin film coats the areas where there is no resist and the copper is exposed.
  • the laminate is then immersed for 60 seconds in a bath containing a blocked isocyanate (4 parts, prepared by reacting 2 moles of technical grade tolylene-2,4-diisocyanate first with 2 moles of methylethyl ketoxime then with 1 mole of 1,4-butanediol), water (4 parts) and 2-n-butoxyethanol (12 parts), followed by rinsing in water.
  • a blocked isocyanate (4 parts, prepared by reacting 2 moles of technical grade tolylene-2,4-diisocyanate first with 2 moles of methylethyl ketoxime then with 1 mole of 1,4-butanediol
  • water 4 parts
  • 2-n-butoxyethanol (12 parts) 2-n-butoxyethanol
  • Example 5 The procedure of Example 5 is repeated, replacing the bath in which the laminate is immersed after electrodeposition by a bath containing BEETLE BE 659, a butylated benzoguanamine-formaldehyde resin (70% solution in butanol) (100 parts), morpholine p-toluenesulphonate (10.5 parts), 2-n-butoxyethanol (170 parts) and water (70 parts) and heating the laminate at 130°C instead of 150°C. This procedure gives a clear copper pattern on the laminate base.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • ing And Chemical Polishing (AREA)
EP19900810391 1989-06-07 1990-05-29 Verfahren zur Herstellung eines metallischen Musters auf einem Substrat Withdrawn EP0402315A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898913090A GB8913090D0 (en) 1989-06-07 1989-06-07 Method
GB8913090 1989-06-07

Publications (2)

Publication Number Publication Date
EP0402315A2 true EP0402315A2 (de) 1990-12-12
EP0402315A3 EP0402315A3 (de) 1993-01-13

Family

ID=10658034

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900810391 Withdrawn EP0402315A3 (de) 1989-06-07 1990-05-29 Verfahren zur Herstellung eines metallischen Musters auf einem Substrat

Country Status (6)

Country Link
US (1) US5073233A (de)
EP (1) EP0402315A3 (de)
JP (1) JPH0342893A (de)
KR (1) KR0168050B1 (de)
CA (1) CA2018249A1 (de)
GB (1) GB8913090D0 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2247784A (en) * 1990-07-18 1992-03-11 Nippon Cmk Kk P.C.B. Manufacture with electrodeposited resist
EP0521649A2 (de) * 1991-06-29 1993-01-07 Ciba-Geigy Ag Verfahren zur Herstellung von Mustern

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05205989A (ja) * 1992-01-28 1993-08-13 Hitachi Ltd リソグラフィ法及び半導体装置の製造方法
US5733283A (en) * 1996-06-05 1998-03-31 Malis; Jerry L. Flat loop bipolar electrode tips for electrosurgical instrument
KR100540644B1 (ko) * 1998-02-19 2006-02-28 삼성전자주식회사 마이크로 엑츄에이터 제조방법
TW457403B (en) * 1998-07-03 2001-10-01 Clariant Int Ltd Composition for forming a radiation absorbing coating containing blocked isocyanate compound and anti-reflective coating formed therefrom
US7000313B2 (en) * 2001-03-08 2006-02-21 Ppg Industries Ohio, Inc. Process for fabricating circuit assemblies using electrodepositable dielectric coating compositions
KR20030068079A (ko) * 2003-07-08 2003-08-19 이인기 남성용 기능성 팬티
US7622844B1 (en) * 2003-12-30 2009-11-24 Hipercon, Llc Metal fiber brush interface conditioning
US7923200B2 (en) * 2007-04-09 2011-04-12 Az Electronic Materials Usa Corp. Composition for coating over a photoresist pattern comprising a lactam
JP5069494B2 (ja) * 2007-05-01 2012-11-07 ＡｚエレクトロニックマテリアルズＩｐ株式会社 微細化パターン形成用水溶性樹脂組成物およびこれを用いた微細パターン形成方法
US7745077B2 (en) * 2008-06-18 2010-06-29 Az Electronic Materials Usa Corp. Composition for coating over a photoresist pattern
JP6503206B2 (ja) 2015-03-19 2019-04-17 東京応化工業株式会社 レジストパターン修復方法
US20180046076A1 (en) * 2015-03-23 2018-02-15 Dow Global Technologies Llc Photocurable Compositions for Three-Dimensional Printing
RU2597373C1 (ru) * 2015-04-29 2016-09-10 федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский национальный исследовательский университет информационных технологий, механики и оптики" (Университет ИТМО) Способ получения металлических пленок заданной формы
JP6594049B2 (ja) * 2015-05-29 2019-10-23 東京応化工業株式会社 レジストパターン形成方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192377A2 (de) * 1985-02-19 1986-08-27 Minnesota Mining And Manufacturing Company Nichtphotoempfindliche Übertragungsschutzschicht
EP0250366A2 (de) * 1986-06-18 1987-12-23 Ciba-Geigy Ag Verfahren zur Herstellung metallischer Strukturen
EP0261301A2 (de) * 1986-09-22 1988-03-30 Ube Industries, Ltd. Verfahren zur Herstellung einer gedruckten Leiterplatte mit durchplattierten Löchern
EP0294325A2 (de) * 1987-05-30 1988-12-07 Ciba-Geigy Ag Verfahren zur Herstellung von metallischen Mustern
EP0326516A2 (de) * 1988-01-27 1989-08-02 Ciba-Geigy Ag Verfahren zur Herstellung von Mustern

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1720610A1 (de) * 1967-01-27 1971-06-16 Bayer Ag Verfahren zur Herstellung von Einkomponenteneinbrennlacken auf Acrylharzbasis
US4101491A (en) * 1975-02-18 1978-07-18 The B. F. Goodrich Company Ethylenically unsaturated blocked aromatic diisocyanates and polymers thereof
US4125661A (en) * 1976-03-19 1978-11-14 Mona Industries, Inc. Laminated plates for chemical milling
FR2489350A1 (fr) * 1980-09-02 1982-03-05 Corona Peintures Procede et composition pour le revetement multi-couches en mouille/mouille de surfaces electro-conductrices
GB8402937D0 (en) * 1984-02-03 1984-03-07 Ciba Geigy Ag Production of images
US4751172A (en) * 1986-08-01 1988-06-14 Shipley Company Inc. Process for forming metal images

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192377A2 (de) * 1985-02-19 1986-08-27 Minnesota Mining And Manufacturing Company Nichtphotoempfindliche Übertragungsschutzschicht
EP0250366A2 (de) * 1986-06-18 1987-12-23 Ciba-Geigy Ag Verfahren zur Herstellung metallischer Strukturen
EP0261301A2 (de) * 1986-09-22 1988-03-30 Ube Industries, Ltd. Verfahren zur Herstellung einer gedruckten Leiterplatte mit durchplattierten Löchern
EP0294325A2 (de) * 1987-05-30 1988-12-07 Ciba-Geigy Ag Verfahren zur Herstellung von metallischen Mustern
EP0326516A2 (de) * 1988-01-27 1989-08-02 Ciba-Geigy Ag Verfahren zur Herstellung von Mustern

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2247784A (en) * 1990-07-18 1992-03-11 Nippon Cmk Kk P.C.B. Manufacture with electrodeposited resist
EP0521649A2 (de) * 1991-06-29 1993-01-07 Ciba-Geigy Ag Verfahren zur Herstellung von Mustern
EP0521649A3 (en) * 1991-06-29 1993-05-05 Ciba-Geigy Ag Method of making patterns

Also Published As

Publication number Publication date
US5073233A (en) 1991-12-17
JPH0342893A (ja) 1991-02-25
GB8913090D0 (en) 1989-07-26
KR0168050B1 (ko) 1999-04-15
KR910002313A (ko) 1991-01-31
CA2018249A1 (en) 1990-12-07
EP0402315A3 (de) 1993-01-13

Similar Documents

Publication Publication Date Title
US5073233A (en) Method of making a metallic pattern on a substrate
US4746399A (en) Method for making metallic patterns
EP0326516B1 (de) Verfahren zur Herstellung von Mustern
US6331376B1 (en) Organic-solvent-based photocurable resist composition and resist pattern-forming method
US4465760A (en) Production of relief images or resist images by a negative-working method
US5268256A (en) Photoimageable electrodepositable photoresist composition for producing non-tacky films
EP0539714B1 (de) Amphotere Zusammensetzungen
US5098527A (en) Method of making electrically conductive patterns
KR100199478B1 (ko) 금속패턴의 제조방법
JPS62119541A (ja) 放射線重合性混合物、該混合物から製造された記録材料及びレリ−フ記録体の製法
US5073478A (en) Method of making a pattern
US5238554A (en) Method of making patterns
DE68920186T2 (de) Photopolymerisierbare Zusammensetzungen.
US5281449A (en) Method of forming pattern coatings based on a radiation curable composition which contains a resin having both thioether and carboxyl groups
CA1333578C (en) Production of metallic patterns
JPH01105240A (ja) 感光性樹脂組成物および感光性エレメント
US5576148A (en) Process for production of printed circuit board
CA2067921A1 (en) Method of making electrical circuit traces
DE4310759A1 (de) Lichtempfindliche Harzmasse für die Elektroabscheidung vom Negativtyp
JP2001117228A (ja) フォトレジスト用感光性樹脂組成物及びレジストパターン形成方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19900531

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE CH DE ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE CH DE ES FR GB IT LI NL SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19930714